EP3004254B1 - Inorganic red pigment - Google Patents

Inorganic red pigment Download PDF

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Publication number
EP3004254B1
EP3004254B1 EP14806961.0A EP14806961A EP3004254B1 EP 3004254 B1 EP3004254 B1 EP 3004254B1 EP 14806961 A EP14806961 A EP 14806961A EP 3004254 B1 EP3004254 B1 EP 3004254B1
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EP
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Prior art keywords
pigment
sno
pigments
zno
tio
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German (de)
English (en)
French (fr)
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EP3004254A4 (en
EP3004254A2 (en
Inventor
Emily Mbayisi MUTAMBI
Aron WOSYLUS
Christof Kujat
Petra DAMM
Jürgen OSWALD
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0009—Pigments for ceramics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/66—Hue (H*)

Definitions

  • the present invention relates to a pigment based on Color Index (C.I.) Pigment Orange 82, especially a mixed metal oxide pigment based on titanium oxide, zinc oxide, tin oxide comprising tungsten oxide and optionally silica, other metal oxides and/or metal sulfides, a process for manufacturing the same and the use thereof as a colorant in various applications.
  • C.I. Color Index
  • Pigment Orange 82 especially a mixed metal oxide pigment based on titanium oxide, zinc oxide, tin oxide comprising tungsten oxide and optionally silica, other metal oxides and/or metal sulfides, a process for manufacturing the same and the use thereof as a colorant in various applications.
  • Lead chromate molybdate pigments are often used when red colorations are desired.
  • the use of chromate-containing pigments and lead-containing pigments is decreasing due to environmental restrictions and requirements, and organic red pigments like diketopyrrolopyrrole pigments or azo pigments come into consideration in order to replace lead chromate pigments.
  • Organic pigments are often inferior in some performance properties like opacity and durability.
  • Pigments with reddish orange shades based on C.I. Pigment Orange 82 (titanium oxide, zinc oxide and tin oxide) are known.
  • a commercially available pigment is, for example, Sicopal® Orange L 2430.
  • US 4,448,608 discloses colorants with the composition (TiO 2 ) a (ZnO) b (SnO) c (SnO 2 ) d .
  • the crystal structure of the pigments is unknown.
  • pigments of different colors are obtained ranging from yellow and orange hues to green, brown or gray hues.
  • Preferred hues are orange and yellow.
  • Critical for the color is the fraction of Sn(II) (as SnO) in the crystal.
  • the amount of SnO 2 increases (d > 0)
  • the hue is shifted toward yellow. If the fraction of SnO is reduced, the pigments become increasingly lighter and weaker in color until ultimately a white or pale gray pigment results.
  • the presence of elements RE and/or AE leads to a slight color shift toward yellow, as compared to pigments of (TiO 2 ) a (ZnO) b (SnO) c (SnO 2 ) d .
  • an object of the present invention to provide an inorganic pigment exhibiting the desired coloristics like red colorations, high opacity and/or high chroma combined with outstanding performance properties like weather resistance in various applications.
  • An inorganic red pigment has been found which exhibits the desired performance characteristics of good weather resistance, chemical resistance and/or color properties.
  • the invention relates to a pigment comprising titanium oxide, tin oxide, zinc oxide and tungsten oxide, wherein the molar ratios of the oxides correspond to a composition of formula (TiO 2 ) a (SnO x ) b (ZnO) c (WO 3 ) d (I), wherein
  • the pigment is a pigment of formula (I), wherein 1.1 ⁇ a ⁇ 2.4; 0.5 ⁇ b ⁇ 1.5; 0.4 ⁇ c ⁇ 1.1; and 0.1 ⁇ d ⁇ 0.6; more preferably, wherein 1.3 ⁇ a ⁇ 2.1; 0.5 ⁇ b ⁇ 1.4; 0.4 ⁇ c ⁇ 1.1; and 0.1 ⁇ d ⁇ 0.5.
  • the pigment comprises one or more oxides and/or sulfides.
  • the invention relates to a pigment comprising titanium oxide, tin oxide, zinc oxide and tungsten oxide and optionally at least one oxide (E y O z ) and/or sulfide, wherein the molar ratios of the oxides correspond to a composition of formula (TiO 2 ) a (SnO x ) b (ZnO) c (WO 3 ) d (I), wherein
  • the optional oxide (E y O z ) may be an oxide like SiO 2 or a metal oxide.
  • Suitable metal oxides may be derived from alkali metals, alkaline earth metals, Al, Ga, In, Ge, Sb, Bi, or transition metals like Zr, Hf, V, Nb, Ta, Mo, Cr, Mn, Fe, Co, Ni, Cu, or rare earth metals like Y, La, Ce or Eu.
  • Suitable examples of alkali metals are Na, K, Rb, and Cs, preferably K.
  • Suitable examples of alkaline earth metals are Mg, Ca, Sr and Ba, preferably Ca and Ba.
  • the optional sulfide may be a sulfide of Zn, Sn, E or a combination thereof.
  • the present invention preferably relates to a pigment of empirical composition of formula (TiO 2 ) a (SnO x ) b (ZnO) c (WO 3 ) d (I) or of formula (TiO 2 ) a (SnO x ) b (ZnO) c (WO 3 ) d (E y O z ) e (II), wherein
  • the pigment is a pigment of formula (II), wherein 1.1 ⁇ a ⁇ 2.4; 0.5 ⁇ b ⁇ 1.5; 0.4 ⁇ c ⁇ 1.1; 0.2 ⁇ d ⁇ 0.6; and 0 ⁇ e ⁇ 0.3.
  • E y O z may be an oxide of an element selected from Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sb, Bi, Zr, Hf, V, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Y, La, Ce, Eu or a combination thereof.
  • the pigment comprises a composition of formula (II), wherein E y O z is an oxide of K, Mg, Ca, Sr, Ba, Al, Si, Bi, Mn, Nb, V, Ta or a combination thereof, preferably an oxide of K, Ca, Ba, Si, Mn, Nb, V or a combination thereof.
  • the pigment may comprise at least one sulfide.
  • SnO x may be partially replaced by the corresponding sulfide SnS x in the pigment of formula (I) or (II).
  • SnS x may comprise SnS and SnS 2 in a molar ratio of SnS : SnS 2 of from 0.7 : 0.3 to 1 : 0.
  • the molar ratio of SnO x to SnS x may be in the range of from 2.0 : 0 to 1.5 : 0.5.
  • ZnO may be partially replaced by ZnS in the pigment of formula (I) or (II). It is also possible that SnO x and ZnO are partially replaced.
  • the molar ratio of ZnO to ZnS may be in the range of from 1.3 : 0 to 1.0 : 0.3.
  • a pigment of formula (II) is preferred, wherein ZnO is partially replaced by ZnS and the molar ratio of ZnO to ZnS is in the range of from 1.25 : 0.05 to 1.0 : 0.3.
  • a pigment of formula (II) is preferred, wherein SnO x is partially replaced by SnS x and the molar ratio of SnO x to SnS x may be in the range of from 2.0 : 0.05 to 1.5 : 0.5.
  • E y O z may be partially or completely replaced in the pigment of formula (II) by the corresponding sulfide E y S z .
  • E y S z may be selected from K, Mg, Ca, Sr, Ba, Al, Bi, Mn, V, Nb or Ta, preferably from Ca, Ba or Mn.
  • the molar ratio of E y O z to E y S z within formula (II) may be in the range of from 0.5 : 0 to 0 : 0.5, preferably 0.49 : 0.01 to 0.01 : 0.49.
  • E in E y O z and E y S z may be the same or different within the pigment of formula (II).
  • a pigment of formula (II) is preferred, wherein the pigment comprises a sulfide of Zn, Sn, Ca, Ba or Mn, preferably E y S z is selected from ZnS, SnS x , CaS, BaS, and/or MnS.
  • the pigment of the invention comprises only one kind of sulfide.
  • the pigment of formula (II) does not comprise a sulfide.
  • the invention preferably relates to a pigment of empirical composition of formula (TiO 2 ) a (SnO x ) b (ZnO) c (WO 3 ) d (E y O z ) e (II), wherein
  • the pigment of the invention comprises E y S z
  • the pigment may comprise E y O z , wherein E is selected from Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sb, Bi, Zr, Hf, V, Nb, Ta, Mo, Cr, Mn, Fe, Co, Ni, Cu, Y, La, Ce, Eu or a combination thereof, and E y S z , wherein E is selected from Ca, Ba, Mn or a combination thereof.
  • the pigment of the invention may comprise E y O z , wherein E is selected from K, Mg, Ca, Sr, Ba, Al, Si, Bi, Mn, Nb, V, Ta or a combination thereof, and E y S z , wherein E is selected from Ca, Ba, or Mn.
  • E is selected from K, Mg, Ca, Sr, Ba, Al, Si, Bi, Mn, Nb, V, Ta or a combination thereof
  • E y S z wherein E is selected from Ca, Ba, or Mn.
  • the pigment may only comprise E y S z , wherein E is selected from Ca, Ba, or Mn.
  • the pigment comprises a composition of formula (II), wherein E y O z is K 2 O and optionally an oxide of Mg, Ca, Sr, Ba, Al, Si, Bi, Mn, Nb, V, Ta or a combination thereof, preferably one oxide thereof.
  • An especially preferred pigment is a pigment of empirical composition of formula (II) wherein E y O z is K 2 O and SiO 2 .
  • E y O z is an oxide of K, Mg, Ca, Sr, Ba, Al, Si, Bi, Mn, Nb, V, Ta or a combination thereof
  • the pigment does preferably not comprise a sulfide.
  • pigment of empirical composition of formula and the term “pigment of formula” used herein are used equally.
  • the variables a, b, c, d, e, f and g correspond to the molar ratios of the oxides and optional sulfides comprised in the pigment of the various formulae described within the pigments of the invention.
  • a pigment of formula (I) or (II) is preferred, wherein 0.01 ⁇ d ⁇ 0.6, especially 0.1 ⁇ d ⁇ 0.5, in particular 0.1 ⁇ d ⁇ 0.4.
  • a pigment of formula (II) is preferred, wherein c and e are each independently from one another: 0.4 ⁇ c ⁇ 0.7; and 0.01 ⁇ e ⁇ 0.3;
  • the metals and/or elements are generally present as ions balanced with the corresponding amount of anions, usually of oxides and/or sulfides.
  • tungsten is present as WO 3 .
  • minor amounts of other oxides may be present like W 10 O 29 , W 4 O 11 and/or WO 2 in an amount up to 10 mol%, based on 1 mol WO 3 , preferably up to 5 mol%, more preferably up tp 98 mol%.
  • the element E which may be selected from the group consisting of Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sb, Bi, Zr, Hf, V, Nb, Ta, Mo, Cr, Mn, Fe, Co, Ni, Cu, Y, La, Ce, and Eu, may occur as purely divalent oxides EO, purely trivalent oxides E 2 O 3 , purely tetravalent oxides EO 2 , purely pentavalent oxides E 2 O 5 , or purely hexavalent oxides EO 3 , and also as oxides with mixed oxidation states.
  • the divalent element E(II) may also comprise the trivalent E(III), or the trivalent E(III) may also comprise the tetravalent E(IV), or the tetravalent E(IV) may also comprise the pentavalent E(V).
  • the stoichiometric composition may vary between between EO and E 2 O 3 and/or between E 2 O 3 and EO 2 and/or between EO 2 and E 2 O 5 and/or between E 2 O 5 and EO 3 . That is, for y is 1, z varies from 1 to 3. The same applies to the corresponding sulfides, if present.
  • the alkali metals are generally present in the pigment of the invention as E(I) oxides, the alkaline earth metals are generally present as E(II) oxides.
  • Aluminum, gallium and indium are generally present as Al 2 O 3 , Ga 2 O 3 and In 2 O 3 , respectively.
  • Silicon and germanium are generally present as SiO 2 and GeO 2 , respectively.
  • Sb is generally present as Sb(V) and optionally in minor amounts as Sb(III).
  • Bi is generally present Bi(III) and optionally in minor amounts of Bi(V).
  • Zirconium and hafnium are generally present as ZrO 2 and HfO 2 , respectively.
  • Manganese is generally present as MnO and optionally in minor amounts of Mn 2 O 3 , or MnO 2 .
  • Vanadium, niobium and tantalum are generally present as V 2 O 5 , Nb 2 O 5 and Ta 2 O 5 , respectively and optionally in minor amounts of VO 2 , V 2 O 3 , VO, NbO, Nb 2 O 3 , NbO, and TaO 2 resp..
  • Chromium is generally present in Cr 2 O 3 and optionally in minor amounts as CrO, CrO 3 and CrO 2 .
  • Molybdenum is generally present as Mo(VI) and optionally in minor amounts of Mo(II), (III) and/or Mo(IV).
  • Iron is generally present as Fe(III) and optionally in minor amounts FeO and/or Fe 3 O 4 .
  • Copper may be present as Cu(II) and optionally in minor amounts as Cu(I).
  • Cobalt may be present as CoO and CO 3 O 4 .
  • Nickel is generally present as NiO. Minor amount means up to 5 mol%, based on the 1 mol of the oxide which is mentioned as generally present.
  • the elements yttrium and lanthanum are generally present as Y 2 O 3 and La 2 O 3 , respectively.
  • Cerium is generally present as CeO 2 .
  • Europium is generally present as EuO.
  • the corresponding sulfides are generally present in the state as mentioned for the oxides, if present.
  • E y O z comprises within formula (II) oxides selected from K 2 O, MgO, CaO, SrO, BaO, Al 2 O 3 , SiO 2 , Bi 2 O 3 , MnO, Nb 2 O 5 , V 2 O 5 , Ta 2 O 5 or a combination thereof.
  • the pigment consists essentially of titanium oxide, tin oxide, zinc oxide and tungsten oxide, wherein the molar ratios of the oxides correspond to the composition of formula (TiO 2 ) a (SnO x ) b (ZnO) c (WO 3 ) d (I), wherein
  • the term "consists essentially” used herein means that the total amount of titanium oxide, tin oxide, zinc oxide and tungsten oxide is ⁇ 95% by weight, based on the total amount of the pigment. Further components may be present in an amount of ⁇ 5% by weight, based on the total weight of the pigment, preferably ⁇ 3% by weight. Further components may be E y O z , E y S z , ZnS, SnS x or other metals as doping materials in titanium oxide, tin oxide, zinc oxide or tungsten oxide.
  • the pigments of the invention usually comprises tin mainly as Sn(II) oxide and optionally as Sn(IV) oxide.
  • SnO x (x varies from 1 to 2) comprises SnO and SnO 2 , wherein the molar ratio of SnO : SnO 2 in SnO x is of from 0.70 : 0.30 to 1.0 : 0, preferably 0.75 : 0.25 to 0.98 : 0.02, more preferably 0.75 : 0.25 to 0.95 : 0.05, most preferably 0.80 : 0.20 to 0.90 : 0.10.
  • An amount of SnO 2 up to 30 mol% may be present when an oxidizing atmosphere or small amounts of oxygen is present during the production process.
  • SnO 2 may also be added in the process of the invention, for example up to 30 mol%, based on 1 mol of SnO. The same applies to SnS 2 .
  • the pigments of the invention may also comprise one or more coating layers.
  • the layer is preferably a transparent layer.
  • the layer may be inorganic and/or organic.
  • a preferred layer is, for example, an inorganic coating selected from SiO 2 , TiO 2 , Fe 3 O 4 , Al 2 O 3 , Bi 2 O 3 or a combination thereof.
  • a preferred coating is based on SiO 2 .It is also possible to have more layers based on SiO 2 .
  • SiO 2 may be present in an amount of at least 2% of weight, preferably 2 to 10% by weight, based on the total weight of the coated pigment.
  • a coating of organopolysiloxane or a wax may also be used, for example dimethylpolysiloxane.
  • an internal SiO 2 layer and an external organopolysiloxane layer may be used.
  • the pigments of the invention may be prepared in accordance of the procedure described in WO-A-2008/083897 .
  • the oxidic raw materials TiO 2 , SnO, ZnO, WO 3 and, if appropriate, SnO 2 , E y O z or precursors of any of these materials are mixed in the form of dry powders.
  • corresponding sulfides or precursors thereof may be added and mixed.
  • the mixture is calcined at temperatures between 600 and 950°C. Calcining may be done in an inert gas atmosphere like nitrogen or argon atmosphere, or in a reducing atmosphere like ammonia or carbon monoxide, or in an oxidizing atmosphere like steam.
  • the resulting furnace clinker is ground, and the resulting particles are optionally coated.
  • oxide precursors which are transformed into oxides by heating.
  • oxide precursors may be hydroxides, carbonates, oxide hydrates, and basic carbonates of the stated elements.
  • Suitable precursors for sulfides may be the corresponding sulfates.
  • the invention is directed to a process for producing a pigment as defined in any aspect herein-before, which process comprises the steps of
  • Optional oxides or sulfides may be added in the mixing step a). At least one compound selected from E y O z , SnO 2 , SnS, ZnS or E y S z , or a precursor compound thereof may be added and mixed as a dry powder.
  • Calcining may be done under an inert gas atmosphere or reducing atmosphere or oxidizing atmosphere.
  • the calcining step may be performed under inert gas atmosphere.
  • the calcining temperature is preferably of from 700 to 875°C or 750 to 875°C.
  • After calcining the furnace clinker is cooled, for example, under inert gas.
  • the furnace clinker is preferably ground by wet milling.
  • H 2 WO 4 is used as starting material to form WO 3 .
  • TiO 2 doped with W can also be employed to form WO 3 in the instant pigments.
  • H 2 WO 4 and TiO 2 doped with W may be used in combination.
  • TiO 2 may be used as rutile or anatase modification.
  • the optional coating step d) may be carried out by methods known in the art, for example as described in US 4,851,049 , US 4,063,956 , US-B-6,423,131 or US-A-5,851,587 .
  • the coating may be prepared by precipitating a SiO 2 -containing layer onto the pigment particles in an aqueous suspension at an elevated temperature of about 70 to 100°C from an aqueous alkali metal silicate solution.
  • the coating may be carried out with ground particles obtained in step c) or may be done under wet grinding conditions.
  • the invention relates to a pigment obtainable by the process as defined herein-before. Accordingly, the invention relates to a pigment obtainable by a process for producing a pigment as defined hereinbefore in formula (I) or (II), which process comprises
  • the particle size of the instant pigments may be of from 0.5 to 3 ⁇ m, preferably 0.6 to 2.0 ⁇ m.
  • the particle size may be measured according to DIN 13320.
  • An alternative possibility is to produce the pigments of the invention by dissolving the salts of the elements titanium, tin, zinc, tungsten and optionally E in water with addition of an acid or a base in a non-oxidizing, inert atmosphere (e.g., nitrogen or argon atmosphere), precipitating the hydroxides or oxide hydrates of titanium, tin, zinc, tungsten and optionally E by addition of aqueous alkali metal hydroxide solution, heating to a temperature below the melting point of alkali metal hydroxides, filtering, washing, drying, and calcining at a temperature of from 750 to 950°C in an inert gas atmosphere.
  • a non-oxidizing, inert atmosphere e.g., nitrogen or argon atmosphere
  • precipitating the hydroxides or oxide hydrates of titanium, tin, zinc, tungsten and optionally E by addition of aqueous alkali metal hydroxide solution, heating to a temperature below the melting point of alkali metal hydroxides
  • the pigments of the invention may be employed diversely as colorants. Preferred fields of use of the pigments are as colorants for coloring paints, printing inks, liquid inks, plastics, rubber, fibers, films and cosmetic formulations. Paints are aqueous or solvent-borne coating materials and also powder coating materials, in which the pigments of the invention may be employed alone or in combination with extenders, white pigments, chromatic pigments or black pigments. Binders that may be used include all of the binders that are usual in the coatings sector. Examples of coating materials which may be colored with the pigments of the invention include more particularly:
  • Effect pigments include platelet-shaped metallic and/or oxidic effect pigments.
  • the pigments of the invention may also be used with advantage to color customary plastics and blends of plastics, either as pigments alone or in combination with white, chromatic, and black pigments, and in combination with all typical additives and stabilizers.
  • Suitable plastics include unplasticized and plasticized PVC, polyolefins, and also all engineering plastics such as ABS, polystyrene, polyamide, polyester, polycarbonate, polyetherketone, and also polyurethanes and rubber systems.
  • the pigments can be incorporated by means of typical mixing, blending, kneading and extrusion techniques.
  • the pigments are chemically inert and highly weather- and temperature-resistant, so making them equally suitable for interior and exterior applications.
  • the pigments of the invention exhibit high reflectivity in the near infrared region and hence can be used with advantage, alone or in a mixture with further suitable pigments and extenders, in those paint materials or plastics particles which under insulation are intended to limit the heating-up of interior spaces (e.g., of buildings and vehicles).
  • the following pigments are suitable for mixtures with white pigments: C.I. Pigment White 4, 5, 6 and 7.
  • the following pigments are suitable for mixtures with black pigments:
  • the following pigments are suitable for mixtures with inorganic chromatic pigments:
  • Organic chromatic pigments suitable for mixtures include, for example, pigments selected from the group consisting of monoazo, disazo, disazo condensation, anthanthrone, anthraquinone, anthrapyrimidine, quinacridone, quinophthalone, diketopyrrolopyrrole, dithioketopyrrolopyrrole, dioxazine, flavanthrone, indanthrone, isoindoline, isoindolinone, isoviolanthrone, perinone, perylene, phthalocyanine, pyranthrone, pyrazoloquinazolone, indigo, thioindigo, triarylcarbonium pigments and combinations thereof. Suitable examples include the following:
  • the pigment mixtures comprise 10% to 99% by weight of the further organic and/or inorganic pigments and 1% to 90% by weight of the pigments of the invention, based on the total weight of pigments.
  • Suitable platelet-shaped pigments include the following:
  • the pigment mixtures comprise 10% to 99% by weight of the platelet-shaped pigments and 1% to 90% by weight of the pigments of the invention, based on the total weight of pigments.
  • the invention relates to a pigment mixture comprising
  • the invention relates to the use of the pigment as defined in any aspect herein-before or the pigment mixture as defined herein-before for coloring paints, printing inks, liquid inks, cosmetics, plastics, films, fibers, glazes for ceramics and glass.
  • the invention relates to paints, printing inks, liquid inks, cosmetics, plastics, films, fibers, glazes for ceramics and glass, which are colored with a pigment as defined in any aspect herein-before or the pigment mixture as defined herein-before.
  • the pigments of the invention exhibit a red coloration which is comparable to colorations currently available with lead chromate molybdate pigments. That is, a suitable and environmental-friendly replacement may be provided.
  • the pigments of the invention incorporated in a mass tone paste (40% by weight of dinonyl phthalate and 60% by weight of PVC, as described in the Examples) are characterized by a hue of less than 57, preferably less than 51 (measured according to the CIELAB system).
  • the presence of WO 3 within the pigments of the invention leads to noticeably more red pigments compared to the pigments of WO-A-2008/083897 .
  • the pigments of the invention have high opacity and high chroma combined with outstanding performance properties like excellent weather resistance and light stability.
  • the pigments are more stable than lead chromate molybdate pigments with regard to light stability, heat stability, weather resistance, acid and alkali stability.
  • the present invention yields strongly colored pigments of high brilliance.
  • the pigments are produced using commercially available metal oxides or corresponding precursors.
  • the molar ratios mentioned in the formulae of the Examples correspond to the molar ratios employed in the process.
  • the pigments are synthesized in a rotating quartz flask with a capacity of 500 ml, located within an electrically heated clamshell furnace.
  • the flask is sealed with a stopper which has openings for a gas supply tube and a gas removal tube and also for a thermocouple.
  • the thermocouple regulates the temperature of the clamshell furnace.
  • a stream of nitrogen is passed through the flask at a constant metering rate of 20l/h (srtp).
  • the contents of the quartz flask are rendered inert with nitrogen for half an hour, during which the flask is rotated, and then heating takes place at 800°C over the course of 1 hour, and this temperature is maintained for 1 hour.
  • the flask is cooled to room temperature (20-25°C).
  • the calcined pigment (furnace clinker) is subsequently ground.
  • a porcelain mortar with a capacity of 500 ml is charged with 30 g of mixed furnace clinker together with 60 g of drinking water and 250 g of glass grinding beads (2 mm in diameter) and grinding is carried out for 10 minutes at 400 revolutions in a vibratory mill (from Retsch).
  • the grinding beads are separated from the pigment suspension by sieving.
  • the suspension is filtered, followed by washing (3x), drying at 160°C in a forced-air drying oven for 1 hour and subjecting to deagglomeration for 15 sec in a Braun mixer.
  • pigment dispersions in PVC plastisol paste are prepared which are cured by 15-minute heating at 160°C in a forced-air drying oven. After the curing procedure, the pigmented plastisol is subjected to colorimetry using an Optronic Multiflash spectrophotometer. The pigments are measured in masstone (chromatic pigment only) for hue h, chroma C* and lightness L*, and in white reduction, consisting of 1 part of chromatic pigment + 3 parts of rutile Kronos 1001 (corresponding to a reduction of 1:4, for color equivalents (CE)).
  • composition of the plastisol 40 parts by weight dinonyl phthalate (Palatinol® N) and 60 parts by weight PVC (Vestolit® 7012).
  • chromatic pigment 0.6 g are dispersed with 6 g of plastisol on a JEL 25.86 plate-type muller (from Engelsmann) with 100 revolutions under a weight of 50 kg.
  • the resulting chromatic pigment paste is applied in a film thickness of 800 ⁇ m to a glass plate by means of a flat coating bar in a film coating apparatus (from Erichsen) and is cured after a short flash-off time in a forced-air drying oven at 160° C for 15 minutes.
  • 0.15 g of chromatic pigment and 0.45 g of rutile pigment are dispersed with 6 g of plastisol on an Engelsmann JEL 25.86 plate-type muller with 150 revolutions under a weight of 70 kg.
  • the chromatic pigment/white paste that results is applied in a film thickness of 800 ⁇ m to a glass plate by means of a flat coating bar in a film coating apparatus (from Erichsen) and is cured after a short flash-off time in a forced-air drying oven at 160° C for 15 minutes.
  • the drawdowns After cooling, the drawdowns, still lying on the glass plate, are subjected to colorimetry on the side facing away from the glass, using the multiflash spectrophotometer (from Optronic), and the color strength and CIELab color values L* (lightness), C* (chroma, i.e., cleanness of color) and h* (hue) are calculated using the BCSWIN program (BASF Color System). Evaluation takes place on the data obtained at a measurement angle of 45°.
  • Example 1 (TiO 2 ) 1.6 (SnO) 0.75 (ZnO)(WO 3 ) 0.25
  • Example 2 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.7 (WO 3 ) 0.3
  • Example 2 The procedure of Example 1 is repeated with the amounts of the raw materials given in Table 2, where also the results of the coloristic tests are shown.
  • Table 2 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 19.85 19.66 8.84 11.64 1.6 0.94 0.7 0.3 49.79 65.5 42.09
  • Example 3 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.5 (ZnS) 0.1 (WO 3 ) 0.4
  • Example 1 The procedure of Example 1 is repeated with the amounts of raw materials given in Table 3 (ZnO is partially replaced by ZnS). Table 3 further shows the results of the coloristic tests of the obtained pigment. Table 3 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO ZnS H2WO4 TiO 2 SnO ZnO ZnS WO 3 h* C* L* 18.95 18.77 6.03 1.44 14.81 1.6 0.94 0.5 0.1 0.4 49.65 61.59 41.06
  • Example 4 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.5 (ZnS) 0.2 (WO 3 ) 0.3
  • Example 1 The procedure of Example 1 is repeated with the amounts of raw materials given in Table 4 (ZnO is partially replaced by ZnS). Table 4 further shows the results of the coloristic tests of the obtained pigment. Table 4 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO ZnS H 2 WO 4 TiO 2 SnO ZnO ZnS WO 3 h* C* L* 19.69 19.50 6.27 3.0 11.54 1.6 0.94 0.5 0.2 0.3 50.55 64.8 42.87
  • Example 5 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.5 (WO 3 ) 0.2 (MnO) 0.3
  • Example 1 The procedure of Example 1 is repeated with the amounts of metal salts given in Table 5 (ZnO is partially replaced by MnO). Table 5 further shows the results of the coloristic tests of the obtained pigment. Table 5 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H2WO4 MnCO 3 TiO 2 SnO ZnO WO 3 MnO h* C* L* 20.21 20.01 6.43 7.90 5.45 1.6 0.94 0.5 0.2 0.3 56.77 66.98 48.18
  • Example 6 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.7 (WO 3 ) 0.3
  • Example 7 (TiO 2 ) 1.6 (SnO) 0.74 (ZnO)(WO 3 ) 0.23
  • Example 7 The procedure of Example 1 is repeated with the amounts of components given in Table 7 (TiO 2 doped with 5 mol% of W is used in addition to H 2 WO 4 ). Table 7 further shows the results of the coloristic tests of the obtained pigment. Table 7 Initial mass (g) Molar ratio Mass tone TiO 2 doped with W SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 24.82 17.42 14.22 6.54 1.6 0.74 1 0.23 47.6 61.35 42.65
  • Example 8 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.725 (WO 3 ) 0.275
  • Table 8 shows the amounts of the raw materials employed and the results of the coloristic tests of the obtained pigment.
  • Table 8 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 21.75 21.55 10.04 11.67 1.6 0.94 0.725 0.275 50.96 67.15 43.92
  • Example 9 (TiO 2 ) 1.6 (SnO) 0.8 (ZnO) 0.725 (WO 3 ) 0.275
  • Example 9 The procedure of Example is repeated with the amounts of raw materials given in Table 9, where also the results of the coloristic tests of the obtained pigment are shown.
  • Table 9 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 22.88 19.29 10.56 12.27 1.6 0.80 0.725 0.275 48.07 56.95 40.42
  • Example 10 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.725 (WO 3 ) 0.275
  • Table 10 shows the amounts of the raw materials employed and the results of the coloristic tests of the obtained pigment.
  • Table 10 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 21.75 21.55 10.04 11.67 1.6 0.94 0.725 0.275 50.27 66.21 43.41
  • Example 11 (TiO 2 ) 1.6 (SnO) 1.1 (ZnO) 0.725 (WO 3 ) 0.275
  • Table 11 shows the amounts of the raw materials employed and the results of the coloristic tests.
  • Table 11 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 20.59 23.87 9.50 11.04 1.6 1.1 0.725 0.275 53.47 72.43 46.18
  • Example 12 (TiO 2 ) 1.4 (SnO) 0.75 (ZnO)(WO 3 ) 0.25
  • Example 1 The procedure of Example 1 is repeated with the amounts of raw materials given in Table 12, where also the results of the coloristic tests of the obtained pigment are shown.
  • Table 12 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 22.30 17.63 14.83 11.36 1.4 0.75 1 0.25 47.92 62.42 42.17
  • Example 13 (TiO 2 ) 1.8 (SnO) 0.75 (ZnO)(WO 3 ) 0.25
  • Example 1 The procedure of Example 1 is repeated with the amounts of raw materials given in Table 13, where also the results of the coloristic tests of the obtained pigment are shown.
  • Table 13 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 24.11 16.94 13.61 10.34 1.8 0.75 1 0.25 48.14 60.31 43.1
  • Example 14 (TiO 2 ) 1.6 (SnO) 0.665 (ZnO)(WO 3 ) 0.275
  • Example 1 The procedure of Example 1 is repeated with the amounts of raw materials given in Table 14, where also the results of the coloristic tests of the obtained pigment are shown.
  • Table 14 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 22.62 15.85 14.40 12.13 1.6 0.665 1 0.275 47.2 58.36 42.39
  • Example 15 (TiO 2 ) 1.4 (SnO) 0.665 (ZnO)(WO 3 ) 0.275
  • Example 1 The procedure of Example 1 is repeated with the amounts of raw materials given in Table 15, where also the results of the coloristic tests of the obtained pigment are shown.
  • Table 15 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 TiO 2 SnO ZnO WO 3 h* C* L* 20.69 16.57 15.05 12.68 1.4 0.665 1 0.275 47.02 58.63 41.83
  • Example 16 (TiO 2 ) 1.6 (SnO) 0.892 (WO 3 ) 0.25 (ZnO)(SiO 2 )
  • Table 16 shows the amounts of the raw materials employed and the results of the coloristic tests.
  • Table 16 Molar ratio Mass tone TiO 2 SnO ZnO WO 3 SiO 2 h* C* L* 1.6 0.75 1 0.25 1 45.12 54.54 36.72
  • Example 17 (TiO 2 ) 1.6 (SnO) 0.86 (ZnO)(WO 3 ) 0.14
  • Table 17 shows the amounts of the raw materials employed and the results of the coloristic tests.
  • Table 17 Initial mass (g) Molar ratio Mass tone TiO 2 -W SnO ZnO TiO 2 SnO ZnO WO 3 h* C* L* 29.07 21.13 14.80 1.6 0.86 1.0 0.138 55.46 71.0 50.13
  • Example 18 (TiO 2 ) 1.6 (SnO) 0.94 (ZnO) 0.75 (WO 3 ) 0.25 (K 2 O) 0.05
  • Table 18 shows the amounts of the raw materials employed and the results of the coloristic tests.
  • Table 18 Initial mass (g) Molar ratio Mass tone TiO 2 SnO ZnO H 2 WO 4 K 2 CO 3 TiO 2 SnO ZnO WO 3 K 2 O h* C* L* 21.79 21.59 10.40 10.63 0.59 1.6 0.94 0.75 0.25 0.05 52.48 73.84 45.7
  • Example 19 (TiO 2 ) 1.6 (SnO) 0.84 (SnO 2 ) 0.1 (ZnO) 0.75 (WO 3 ) 0.25 (K 2 O) 0.05

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)
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KR102146241B1 (ko) * 2016-05-02 2020-08-21 더 셰퍼드 컬러 컴퍼니 열 안정성, 산성 조건에 대한 내성 및 우수한 내광성을 나타내는, 산화안티몬 및/또는 산화니오븀을 포함하는 핑크색 및 바이올렛색 안료
WO2018042803A1 (ja) * 2016-08-29 2018-03-08 信越化学工業株式会社 コーティング組成物および被覆物品
KR101977321B1 (ko) 2018-12-10 2019-05-10 주식회사 칼라런트코리아 폴리아미드용 고내열성 오렌지계 무기안료의 제조방법 및 이 방법에 의해 제조되는 오렌지계 무기안료
CN110589889B (zh) * 2019-10-12 2021-11-26 景德镇陶瓷大学 一种无机复合橙色颜料及其制备方法
EP3868818A1 (de) * 2020-02-19 2021-08-25 LANXESS Deutschland GmbH Hochvoltkomponenten
CN112048193B (zh) * 2020-09-02 2021-04-30 电子科技大学 一种兼顾低明度和高近红外反射率的绿色颜料及其制备方法
CN115849886A (zh) * 2022-12-02 2023-03-28 北京科技大学 一种高近红外反射蓝色无机颜料及其制备方法

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US4448608A (en) 1982-12-30 1984-05-15 Johnson Matthey Public Limited Company Colored inorganic complex for use as a pigment and compositions containing it
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CN101583567B (zh) * 2007-01-12 2013-03-27 巴斯夫欧洲公司 包含锡和稀土元素的颜料
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KR102280563B1 (ko) 2021-07-23
US20160108247A1 (en) 2016-04-21
EP3004254A4 (en) 2017-03-15
MX2015016733A (es) 2016-08-03
CN105246981A (zh) 2016-01-13
KR20160014632A (ko) 2016-02-11
WO2014195829A3 (en) 2015-04-23
JP6410806B2 (ja) 2018-10-24
EP3004254A2 (en) 2016-04-13
WO2014195829A2 (en) 2014-12-11
ES2690788T3 (es) 2018-11-22
CN105246981B (zh) 2018-02-09

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